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UNIVERSITI PUTRA MALAYSIA

PREPARATION AND PHYSICOCHEMICAL PROPERTIES OF

ZINC OXIDE NANOPARTICLES

KHAIRUL BASYAR BIN BAHARUDIN

ITMA 2011 20

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PREPARATION AND PHYSICOCHEMICAL PROPERTIES OF

ZINC OXIDE NANOPARTICLES

By


Thesis Submitted to the School of Graduated Studies,

Universiti Putra Malaysia, in Fulfillment of the Requirement for the Degree of

Master of Science

April 2011

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Abstract of thesis presented to the Senate of University Putra Malaysia in

fulfilment of the requirement for the degree of Master of Science

PREPARATION AND PHYSICOCHEMICAL PROPERTIES OF ZINC OXIDE

NANOPARTICLES.

By


April 2011

Chairperson : Professor Mohd Zobir bin Hussein, PhD

Institute : Institute of Advanced Technology

Zinc oxide nanoparticles are important inorganic particles which receive great interest

over the past few years because of the wide nanotechnology application in various fields

of material physics and chemistry. The physicochemical properties of resulting ZnO

nanoparticles can be controlled by the synthesis route, method of preparation and

parameters related to condition processing. In this study, ZnO nanoparticles were

successfully synthesized by three different methods namely polyol method, solvothermal

method and co-precipitation method. X-ray diffraction (XRD) patterns show that the all

resulting ZnO nanoparticles materials which were synthesized by all the three different

methods are pure phase with good crystalinity and completely matched the hexagonal-

wurzite structure. The presence of a broad and sharp absorption band at around 440 cm-1

in the FTIR spectrum further confirmed the existence of ZnO phase.

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In polyol method, ZnO nanoparticles were successfully synthesized under hydrothermal

condition. Zinc acetate (ZnAc) was dissolved and heated in three different glycol

solutions, namely ethylene glycol (EG), diethylene glycol (DEG) and trietyleneglycol

(TEG). The effect of different glycol solutions and calcination on the formation of ZnO

nanoparticles was investigated. Single-modal narrow particle size distribution of ZnO

nanoparticles with average particles size of 2 ± 1 nm, 12 ± 1nm and 13 ± 1 nm were

obtained when EG, DEG and TEG were used in the synthesis, respectively. The

broadness of the size distribution of the ZnO nanoparticles can be given as

EG > DEG >TEG. The specific surface areas of all the resulting materials however show

very similar values ranging from 12.2 to 13.5 m2g

-1.

The low-temperature solvothermal process was employed as the second method to

synthesize ZnO nanoparticles. The initial concentration of zinc acetate was controlled

and this process is based on the decomposition of zinc acetate and sodium hydroxide

(NaOH) in a mixture solution of ethanol and EG. The effect of different zinc acetate

concentration and the effect of organic solvent mixtures solution between ethanol and

EG can be shown by a single modal narrow particle size distribution with the average

size below 25 ± 1 nm. Field emission scanning electron microscopy (FESEM) and

transmission electron microscopy (TEM) analysis revealed that less macroscopic

agglomeration of ZnO nanoparticles, indicating that the effect of low temperature

process in the mixtures solution also contributed to the higher specific surface area of

about 40 m2g

- 1. Further effect of high calcinations temperature on the physicochemical

properties of the resulting ZnO nanoparticles shows more crystalline and pure phase.

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However, the increasing particles size resulted in the decreasing of specific surface area

due to the compact agglomeration of ZnO particles.

Lastly, an intermediate zinc oxalate phase was synthesized by oxalate coprecipitation

from nearly saturated solution of zinc acetate and 2-propanol of oxalic acid solution.

Highly crystallized and pure phase ZnO nanoparticles were successfully synthesized by

thermal treatment at 400 to 600 o

C for 4 hours. Single-modal narrow particle size

distribution of ZnO nanoparticles with the average particles size of 3± 1 nm , 28 ± 1 nm

and 25 ± 1 nm are obtained at 400, 500 and 600 o

C, respectively. FESEM and TEM also

revealed the different surface structure and morphology of ZnO nanoparticles obtained at

calcination temperatures. A huge reduction of specific surface area of ZnO nanoparticles

from 22.9 m2g

-1 to 2.6 m

2g

-1 was observed when the calcination temperature is increased

from 400 to 600 oC.

This study verified, a good crystallinity, high purity, small particle size and large

specific surface area of ZnO nanoparticles can be obtained using all the methods. The

effect of preparation parameters in each method gives the most influence to

physichochemical properties of the resulting material.

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai

memenuhi keperluan untuk ijazah Master Sains

PENYEDIAN DAN SIFAT KIMIA-FIZIKAL PARTIKEL NANO ZINK OKSIDA

Oleh


April 2011

Pengerusi : Profesor Mohd Zobir Bin Hussein, PhD

Institut : Institut Teknologi Maju

Partikel nano Zink oksida adalah partikel tak organik penting yang menerima perhatian

tinggi dalam tahun kebelakangan ini kerana mempunyai aplikasi nanoteknologi yang

meluas dalam pelbagai bidang fizik bahan dan kimia. Sifat kimia-fizikal partikel nano

ZnO yang dihasilkan dapat dikawal melalui laluan sintesis, kaedah persiapan dan

parameter yang sesuai dengan keadaan proses. Dalam kajian ini, partikel nano ZnO telah

berjaya disintesis dengan tiga kaedah yang berbeza iaitu kaedah poliol, kaedah

solvoterma dan kaedah ko-pemendapan. Corak pembelauan sinar-X menunjukkan

bahawa semua bahan partikel nano ZnO yang disintesis melalui ketiga-tiga kaedah yang

berbeza menghasilkan hablur yang baik dengan fasa tulen yang bersesuaian dengan

struktur heksagon-wurzite. Kehadiran satu jalur penyerapan yang luas dan tajam sekitar

440 cm-1

pada spectrum FTIR membuktikan lebih lanjut kewujudan fasa ZnO.

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Dalam kaedah poliol, partikel nano ZnO telah berjaya disintesis dalam keadaan

hidroterma. Zink asetat (ZnAc) dilarutkan dan dipanaskan dalam tiga larutan glikol yang

berbeza, iaitu etilina glikol (EG), dietilina glikol (DEG) dan trietilina glikol (TEG).

Kesan terhadap larutan glikol berbeza dan pemanasan pada pembentukan partikel nano

ZnO telah dikaji. Taburan sempit modal tunggal partikel nano ZnO dengan saiz purata

partikel adalah 2, 12 dan 13 nm masing-masing diperolehi semasa EG, DEG dan TEG

digunakan semasa sintesis. Keluasan saiz taburan partikel nano ZnO boleh ditunjukan

dengan urutan EG> DEG> TEG. Luas permukaan khusus semua bahan yang dihasilkan

walaubagaimanapun menunjukkan nilai yang hampir iaitu disekitar 12.2 sehingga 13.5

m2g

-1.

Proses solvoterma suhu rendah digunakan sebagai kaedah kedua untuk sintesis partikel

nano ZnO. Kepekatan awal ZnAc dikawal dan proses ini berdasarkan pada penguraian

ZnAc dan natrium hidroksida (NaOH) di dalam campuran larutan etanol dan EG. Kesan

kepekatan ZnAc yang berbeza dan kesan larutan campuran pelarut organik diantara

etanol dan EG boleh ditunjukkan oleh taburan sempit modal tunggal saiz partikel dengan

ukuran purata di bawah 25 nm. Mikroskopi pengimbasan elektron pancaran medan

(FESEM) dan Mikroskop penghantaran elektron (TEM) analisa mendedahkan bahawa

agelomerasi makroskopik partikel nano ZnO yang kurang, menandakan bahawa kesan

suhu yang rendah dalam campuran larutan juga menyumbangkan terhadap luas

permukaan khusus lebih tinggi iaitu sekitar 40 m2g

-1. Kesan lanjutan terhadap suhu

kalsinasi tinggi pada sifat kimia-fizikal partikel nano ZnO yang dihasilkan menunjukkan

penghasilan fasa hablur dan ketulenan bahan akhir yang lebih tinggi. Namun demikian,

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peningkatan saiz partikel mengakibatkan penurunan luas permukaan khusus kerana

kepadatan agelomerasi partikel ZnO.

Kaedah terakhir, fasa pertengahan zinc oksalat disintesis melalui kopemendapan oksalat

dari larutan hampir tepu ZnAc dengan larutan asid oksalat yang disediakan daripada

pelarut 2-propanol. Penghabluran yang tinggi dan fasa ZnO yang tulen telah berjaya

disintesis dengan pemanasan selama 4 jam pada suhu 400 sehingga 600 o

C.Taburan saiz

modal tunggal sempit partikel nano ZnO dengan saiz purata partikel adalah 3, 28 dan 25

nm diperolehi masing-masing pada 400, 500 dan 600 oC. FESEM dan TEM juga

mendedahkan struktur permukaan dan morfologi partikel nano ZnO yang berbeza

diperolehi dalam suhu kalsinasi yang lebih tinggi. Penurunan besar luas permukaan

khusus partikel nano ZnO dari 22.9 m2g

-1 kepada 2.6 m

2g

-1 diperhatikan ketika suhu

kalsinasi meningkat dari 400 kepada 600 oC.

Kajian mengesahkan semua kaedah penyediaan menghasilkan partikel nano ZnO yang

baik penghabluran, tinggi ketulenan , saiz partikel kecil dan luas permukaan khusus yang

besar. Kesan parameter penyediaan melalui kaedah masing-masing memberikan

pengaruh besar terhadap sifat akhir kimia-fizikal bahan yang dihasilkan

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ACKNOWLEDGEMENT

Alhamdulillah, praise to ALLAH the Almighty for blessing the completion of this study

and to all individuals who contribute to this project.

First of all, I would like to express my sincere gratitude to my project supervisor,

Professor Dr. Mohd Zobir bin Hussein for his valuable advice, excellent guidance, ideas,

kindness and great encouragement throughout this project.

My special appreciation and thanks to the staff of Chemistry Department, Faculty of

Science, UPM, Institute of Advanced Technology UPM, Institute of Bioscience UPM

and lastly Universiti Islam Antrabangsa Malaysia. My appreciation and thanks also goes

to all post graduate students at ITMA and not forgotten the postgraduate students in Old

Chemistry Laboratory 2 for the support and helpful in finishing my project.

To my beloved parents and family, thank you very much for giving me the

encouragement and moral support throughout my study in UPM.

To all my friends and the rest whom have helped to complete my study, ‘THANK YOU’

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I certify that an Examination Committee has met on 19 April 2011 to conduct the final

examination of Khairul Basyar Bin Baharudin on his Master of Science thesis entitled

“Preparation and Physicochemical Properties of Zinc Oxide Nanoparticle” in

accordance with University Pertanian Malaysia (Higher Degree) Act 1980 and

University Pertanian Malaysia (Higher Degree) regulation 1981. The Committee

recommends that the student be awarded the relevant degree.

Members of the examination Committee were as follows:

Wan Mohamad Daud Wan Yusoff, PhD

Associate Professor

Faculty of Science

Universiti Putra Malaysia

(Chairman)

Mansor Hashim, PhD

Associate Professor

Faculty of Science


(Internal Examiner)

Jumiah Hassan, PhD

Associate Professor

Faculty of Science


(Internal Examiner)

Shahidan Radiman, PhD

Professor

School of Applied Physics

Faculty of Science and Technology

Universiti Kebangsaan Malaysia

Malaysia

(External Examiner)

SHAMSUDDIN SULAIMAN, PhD

Professor and Deputy Dean

School of Graduated Studies


Date:

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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been

accepted as fulfillment of the requirement for the degree of Master of Science. The

members of the Supervisor Committee were as follows:

Mohd Zobir Hussein, PhD

Professor

Faculty of Science


(Chairman)

Abdul Halim Abdullah, PhD

Association Professor

Faculty of Science


(Member)

HASANAH MOHD GHAZALI, PhD

Professor and Dean

School of Graduate Studies


Date:

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DECLRATION

I declare that the thesis is my original work except for quotations and citations which has

been duly acknowledgement. I also declare that it has not been previously and is not

concurrently submitted for any other degree at Universiti Putra Malaysia or other

institutions.

KHAIRUL BASYAR BAHARUDIN

DATE: 19 April 2011

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TABLE OF CONTENTS

Page

ABSTARCT ii

ACKNOWLEDGEMENT vii

APPROVAL ix

DECLARATION x

LIST OF TABLES xiii

LIST OF FIGURES xv

LIST OF ABBREVATIONS xix

CHAPTER

1 INTRODUCTION 1

Objective

2 LITERATURE REVIEW

2.1 Metal Oxide 5

2.1.1 Metal Oxide Nanoparticles 6

2.1.2 Physicochemical Properties and Application 7

2.2 Zinc Oxide

2.2.1 Properties of Zinc Oxide 11

2.2.2 Structural features 12

2.2.3 Application of Zinc Oxide 14

2.2.4 Synthesis Of Zinc Oxide Nanoparticles 17

3 MATERIAL AND METHODS

3.1 Material 26

3.2 Synthesis of Zinc Oxide Nanoparticles

3.2.1 Polyol Method Under Hydrothermal Condition 27

3.2.2 Solvothermal Method 29

3.2.3 Co-precipitation Method 31

3.3 Physicochemical Characterization

3.3.1 Powder X-Ray Diffraction (PXRD) 33

3.3.2 Fourier Transform-Infrared Spectroscopy (FTIR) 33

3.3.3 Thermogravimetry Analysis (TGA-DTG) 34

3.3.4 Particles Size Distribution 34

3.3.5 Field Emission Scanning Electron Microscopy (FESEM) 35

3.3.6 Transmission Electron Microscopy (TEM) 35

3.3.7 Surface Area Analysis 35

4 RESULTS AND DISCUSSION

4.1 Zinc Oxide Nanoparticles Synthesized by Polyol Method

Under Hydrothermal Conditio



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4.1.4 Particles Morphology 45


4.2 Zinc Oxide Nnanoparticles Synthesized by Solvothermal Method






4.3 Zinc Oxide Nnanoparticles Synthesized by Co-precipitationl Method


4.3.2 Thermal Studies 85





5 CONCLUSION 100

REFERENCES 102

APPENDICES 111

BIODATA OF STUDENT 113

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